Peroxidized ester



containing a Patented May 18, 1943 UNITED STATES PATENT OFFICE PEROXIDIZED ESTER Maynard C. Agens, Schenectady, N. Y., assignor to General Electric Company, a corporation of New York No Drawing. Application March 27 1940, Serial No. 326,271

6 Claims.

This invention relates broadly to peroxidized esters and to compositions comprising the same. More particularly the invention is concerned with the production and utilization of a peroxidized ester of a polycarboxylic acid, e. g., succinic, maleic, phthalic, tricarballylic, etc., and and an alcohol-ether, e. g., tetrahydrofurfuryi alcohol,

GH2---OH:

ethylene glycol monoethyl ether,-diethylene glycol monophenyl ether, etc. esters are especially suitable for use as polymerization catalysts. The scope of the invention includes compositions of matter comprising a polymerizable organic compqund containing a CH=C/ grouping, specifically a grouping, and a peroxidized ester of a polycarboxylic acid wherein the hydrogen of at least one carboxyl group has been replaced by the radical of an alcohol-ether.

It has been the general practice heretofore in the preparation of polymeric materials from polymerizable organic compounds containing a grouping to efiect polymerization with the aid of a polymerization catalyst, accompanied by heat, light or, heat and light. Various catalysts have been employed or suggested for this purpose, for instance inorganic super-oxides such as barium, peroxide, sodium peroxide, etc., dialkyl peroxides such as lauryl peroxide, stearyl peroxide, etc., symmetrical diacyl peroxides, e. g., acetyl peroxide, lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, etc., unsymmetrical or mixed diacyl peroxides, e. g., acetyl benzoyl peroxide, etc. Illus'- trative examples of other known accelerators of polymerization of polymerizable compounds grouping are given in copending Nordlander application Serial No. 302,166, filed October 31,

1939, and assigned to the same assignee as the- These peroxidized present invention. Bcnzoyl peroxide has been the catalyst heretofore. most commonly used in polymerizing compounds containing a grouping.

There long has been need, particularly in the plastics and coating arts, for a relatively inexpensive, readily producible, efiicient catalyst for polymerizing polymerizable -containing organic compounds. Such catalyst should be readily soluble or dispersible in the material to be polymerized. There should be no that would discolor the polymerized material.

The present invention provides a polymerization catalyst meeting the above requirements. This new polymerization catalyst consists essentially of a peroxidized ester of a polycarboxylic acid containing at least two carbon atoms (preferably from three to eighteen carbon atoms, in-

clusive) wherein the hydrogen of at least one carboxyl group has been replaced by the radical of an alcohol-ether. The other carboxyl group or groups may be unesterifiemespecially when a less active polymerization catalyst is desired. Or, the hydrogen of such carboxyl group 'or groups may be replaced by the radical of an alcohol-ether which is the same as, or different from, the other alcohol-ether substituent grouping, or by the radical of any other esterifiable hydroxy compound. The essential point is that the hydrogen or at least one carboxyl group of the polycarboxylic acid must be replaced by the radical of an alcohol-ether. Optimum results are obtained when the hydrogens of all the carboxyl groups are replaced by the radicals of an alcohol-ether. Hence, in carrying the invention into effect I prefer to use a. peroxidized alcoholether polyester (diester, triester, etc.) of a polycarboxvlic acid.

The alcohol-ether esters of polycarboxylic acids are prepared in accordance with technique well known to those skilled in the art of preparing esters. For example, they may be prepared as described in my copending application Serial No. 326,272, filed concurrently herewith, with reference to the preparation of esteriflcation products of a polyhydric alcohol, an alcoholether containing a single alcoholic hydroxyl group, and an alpha unsaturated alpha beta polycarboxylic acid.

In preparing the polymerization catalysts of this invention, I peroxidize an alcohol-ether ester of a polycarboxylic acid, for instance by heating such ester in contact with air or oxygen. Advantageously the ester is peroxidized by agitating it in air while simultaneously heating it at a suitable temperature, for example at 30 to 100 C. Either mechanical or air agitation may be employed. The ester also may be mechanically stirred while simultaneous?!) passing a stream of air or oxygen into the mass. In some cases it may be desirable to peroxidize the ester in the absence of applied heat, for instance at room temperature to C.). In general, the lower the temperature of peroxidation, the longer the time required; and, conversely, the higher the temperature, the shorter the time..

The degree of peroxidation obtained by the abovedescribed treatment of the esters convenient-ly may be measured by the analytical method described by Liebhafsky and Sharkey in an article The Determination of Organic Peroxides,"

appearing in the January, 1940, issue of the Journal of the American Chemical Society. This method involves the titration of iodine with a sodium thiosulfate solution. peroxidation is expressed as the peroxide equivalent per gram of material. This is defined by Holde in Kohlenwasserstofiiile und Fette, 7th edition, 1933, page 220, as the gram equivalent of active oxygen per gram of material. This may be better understood by a consideration of the following:

gram equivalent of active oxygen; (5) Then, if the weight of the sample be represented by W,

XXY 2000W equals gram equivalent of active oxygen per gram of material, that is, peroxide equivalent per gram of material.

The degree of.

. it in air while simultaneously heating it to a temperature of about 80 C.

Illustrative of the rate of peroxidation are the Peroxide equivalent per gram oi material From a practical standpoint it is desirable that the peroxidized alcohol-ether esters of this invention have a peroxide equivalent per gram of material of at least 8 10, preferably 10- or more.

Catalysts of the peroxide type used for accelerating the polymerization of polymerizable -CH=C/ -containing compounds not only should be stable at normal temperature but furthermore should i not undergo excessive thermal decomposition at the elevated temperatures at which the polymerization is to be carried out. The following data with reference to the peroxide content of peroxidized di-(tetrahydrofurfuryl) maleate when heated at temperatures materially above 80 C. for varying periods of time are illustrative of the action of the peroxidized a1cohol-ether esters of this invention under heat:

Peroxide equivalent per gram of material Initial value 1018x10- After 2 hours heating at 96-97 C 97 x10- After 3 to 4 minutes more at C- 92.5X10- After 10 minutes more at -160 C- 8.4x 10- The above data show that a peroxidized alcohol-ether ester of a polycarboxylic acid, specifically peroxidized di-(tetrahydrofurfuryl) maleate, is relatively stable at temperatures as high as 120 C. and that it only decomposes rapidly at temperatures of the order of 150 to 160 C. These characteristics, together with the fact that this alcohol-ether ester is a relatively nonvolatile liquid which itself is polymerizable, make it especially adapted for the polymerization of polymerizable vinylidene compounds, vinyl compounds, acrylic and alkacrylic compounds, unsaturated alkyd resins, and other polymerizable organic compounds containing a -CH=C/ grouping.

The following examples are illustrative of the utilization of these peroxidized alcohol-ether esters as polymerization catalysts. All parts are by weight.

Example 1 Parts Diethylene glycol maleate 50 Peroxidized di-(tetrahydrofurfuryl) succinate having a peroxide equivalent of 101.'l 10- 50 were mixed in a suitable receptacle, which then was placed in a 130 C. oven. When examined at the end of 15 minutes heating, the mixture had polymerized to a solid condition. Diethylene glycol maleate alone, when heated at a temperature as high as 0., formed a skin upon the surface while the underlying portion was entirely fluid. r

Example 2 Parts Dlallyl itacona 100 Peroxidized di-(tetrahydrofurfuryl) maleate having a peroxide equivalent of 132.5X10' 50 were mixed in a suitable container, which thereafter was placed in a 125 C. oven. After 30 minutes at this temperature the entiremass polymerized to solid state.

Example 3 Parts Diallyl itaconate 90 Peroxidized di-(tetrahydrofurfuryl) maleate having a peroxide equivalent of 132.5

were mixed in a suitable receptacle, which'then was placed in a 120 C. oven for 1 hour. At the end of this time the mixture had polymerized were mixed in a suitable container and placed in an 80 C. oil bath. At the end of- 2 /2 hoursthis mixture had polymerized to a solid condition. A

corresponding treatment of methyl methacrylate alone resulted in a very fluid material showing only very slight polymerization.

Example 5 Parts Methyl methacrylate 60 Peroxidized di-(tetrahydrofurfuryl) maleate having a peroxide equivalent of 132.5 10- v were mixed in a stoppered tube and placed in an 80 C. oil bath. In approximately 1 hour the mixture had polymerized to a solid state. Fur-'- ther heating for about 20 hours at this temperature yielded a flexible, tough compound.

Example 6 Parts Styrene 80 Peroxidized di-(tetrahydrofurfuryl) maleate having a peroxide equivalent of132.5 10- 20 were mixed in a suitable container and heated in an 80 C. oil bath. The viscosity of this mixture slowly increased until at the end of 7 hours it no longer would flow. Additional heating for about 18 hours at this same temperature yielded a tough, transparent material. Similar treatment of styrene alone gave a material of very low viscosity at the end of '7 hours and avi seous syrup uponfurther heating. These comparative results alcohol-ethers may be employed. Specific examples of alcohol-ethers containing a single alcoholic hydroxyl group and. at least one ether linkage are glycol mono-alkyl ethers, e. g., ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc.: also, glycol mono-aryl ethers, e. g., the monophenyl and monobenzyl ethers of ethylene glycol and diethylene, glycol. Additional examples of other monohydric alcohol-ethers which may be used in preparing the alcohol-ether esters oi. this invention are given in my copending application Serial No. 326,272.

In preparing these alcohol-ether esters I may use any saturated or unsaturated polycarboxylic acid containing two or more carboxyl groups. Thus I may use saturated aliphatic polycarboxylic acids such, for example, as oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, tricarballylic, malic, tartaric, citric, etc.; unsaturated aliphatic polycarboxylic acids such, for instance, as maleic, fumaric, citraconic, mesaconic, itaconic, aconitic, etc.; the cyclic polycarboxylic acids, more specifically the saturated and unsaturated cyclo aliphatic polycarboxylic acids, e. g., the cyclopropane and cyclopropene dicarboxylic acids, the cyclohexane and cyclohexene dicarboxylic acids, the alkyl cycloalkane polycarboxylic acids, etc.; and the halogenated and non-halogenated aromatic polycarboxylic acids, e. g., halogenated and non-halogenated phthalic, isophthalic, terephthalic, benzoyl phthalic, diphenic, benzophenone-2,4'-dicarbox-- ylic, etc., acids. Mixtures of difierent polycarboxylic acids may be used. If available, the anhydrides of polycarboxylic acids may be employed. The terms polycarboxylic acids and dicarboxylic acids, as used generally herein and in the appended claims, therefore are intended to include within their meanings the anhydrides of the acids.

I prefer to use as polymerization catalysts peroxidized di-(alcohol-ether) esters of dicarboxylic acids, tri-(alcohol-ether) esters of tricarboxylic acids, etc., that is, peroxidized esters 'ofpolycarboxylic acids wherein all of the hydrogens of the carboxyl groups have been replaced by the radicals of the same or different alcoholethers. With such esters maximum peroxidation per unit weight of material can be obtained. However, in cases where high peroxide content of the ester is of secondary consideration, then I may prepare esters containing the groupingsv (COOR): and (COOR') y, where R is the radical of an alcohol-ether, R is a member of the class consisting of hydrogen andradicals of esterifiable hydroxyl compounds other than alcohol-ethers, and a: and y are positive numbers the sum of which is at least 2. Whensuch mono-esters or mixed esters are prepared from a polycarboxylic the radicals of which may constitute R in the above formulas are the saturated and unsaturated, aliphatic, straight-chain and branchedchain alcohols, e. g., ethyl, propyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, tertiary amyl, allyl, methallyl, propallyl, etc., alcohols; ethylene glycol mono-esters, e. g., ethylene glycol monoacetate, ethylene glycol monopropionate, ethylene glycol monobenzoate, ethylene glycol monocrotonate, etc.; alcohols containing substituent groups, e. g., l-chlorallyl alcohol, 2-chiorallyl alcohol, etc.; polyhydric alcohols'free from ether linkages, e. g., ethylene glycol, propylene glycol, trimethylene glycol, glycerol, pentaery thritol', etc.; the esteriflable carbocyclic organic compounds, e. g., benzyl alcohol, cinnamyl alcohol, cyclopentanol, cyclohexanol, etc. Other examples of'esterifiable hydroxyl compounds which boxylic acids that, when peroxidized, form the preferred polymerization catalysts may be representedby the formula A-(COOR) where A is a polyvalent hydrocarbon radical having at least one carbon atom, R is the radical of an alcoholether, :1: is at least 2, the value of a: being equal to the valence of A.

Theperoxidized alcohol-ether esters of this invention may be used as accelerators of polymerization of polymerizable organic compounds containing a a grouping, illustrative examples of which are esters containing ethylenic or acetylenic unsaturationin either the alcohol radical or the acid radical,

or in both, for instance saturated and unsaturated alcohol esters of unsaturated monocarboxylic and polycarboxylic acids, unsaturated alcohol esters ofhon-ethylenic polycarboxylic acids, unsatu-' rated alcohol esters of saturated monocarboxylic acids, etc. Examples of containing compounds with which these new esters may be copolymerized to yield new compositions of particular utility in the plastics and coating arts are vinyl cyclic compounds, e. g., styrene, methyl styrene, para chloro styrene, divinyl benzene, vinyl naphthalene, vinyl furane, etc.; unsaturated ethers, e. g., ethyl vinyl ether, metha-llyl propyl ether, etc.; unsaturated ketones, e. g.,lmethyl vinyl ketone, divinyl ketone, methyl allyl ketone, etc.; itaconic esters, e. g., dialkyl itaconates, diaryl itaconates, etc.; acrylic and alkacrylic compounds, e. g., acrylic nitrile, methacrylic nitrile, esters of esteriflable acrylic compounds, for instance methyl, ethyl, propyl, butyl, etc. acrylates and alkacrylates, more specific examples of which latter are methyl methacrylate, methyl ethacrylate, .ethyl methacrylate, ethyl ethacrylate, etc.

Additional examples of organic compounds containing a grouping which may be employed, separately or mixed, in forming these new interpolymerizatlon products, are given in the copending applications of Nordlander and Margrave Serial No. 302,184, filed October 31, 1939, Nordlander Serial Noe. 302,165 and 302,166, also filed October 31, 1939, DAlelio Serial No. 313,103, flied January 9, 1940, and in the other copending applications referred to in the said D'Alelio application. All of these copending applications are assigned to the same assignee as the present invention.

From the foregoing description it will be seen that this invention provides a method of preparing a new polymerization catalyst, which method comprises peroxidizing an ester of a polycarboxylic acid wherein the hydrogen of at least one carboxyl group has been replaced by the radical of an alcohol-ether. The alcohol-ether commonly known in the trade as tetrahydrofuriuryl alcohol, but which more properly may be termed a heterocyclic alcohol-ether, yields particularly effective peroxidized esters and therefore is the preferred alcoholether reactant.

The invention also provides a method of polymerizing a polymerizable organic compound containing a grouping, specifically a CHFC/ grouping, which comprises effecting polymerization of such compound while admixed with a polymerization catalyst comprising essentially a peroxidized alcohol-ether ester of a polycarboxylic acid. Polymerization may be eifected at room temperature (20 to 25 C.) or at elevated temperatures, but generally is carried out within the temperature range of 60 to C.

The amount of catalyst will vary widely, depending upon the peroxide content of the particular peroxidized ester and the polymerization characteristics of the particular material to be polymerized. Ordinarily, the amount oiperoxidized ester is within the range of 0.1 to 25%, occasionally as high as 50%, by weight or the whole. The higher amounts conveniently may be employed when using a peroxidized ester of an alpha unsaturated alpha beta polycarboxylic acid, for example maleic acid or anhydride, since such esters are polymerizable alone to solid or semisolid state. I

Although I prefer to use these new peroxidized esters in combination with polymerizable -containing compounds thereby to accelerate the polymerization of the latter, their field of utility is not limited thereto. Thus, they may be used, for example, as modifying agents or various substances commonly employed in the plastics and coating arts, for instance, air-drying and baking coating compositions such as varnishes, enamels, primers, etc., natural and synthetic resins, cellulose derivatives such as the esters and others, e. g., cellulose nitrate, cellulose acetate, propionate, butyrate, etc., methyl cellulose, ethyl cellulose, benzyl cellulose, etc., and for many other purposes.

What I claim as new and desire to secure by Letters Patent of the United States ether of a glycol, said ester having-a peroxide equivalent per gram of material of not less than 4. Peroxidized tetrahydrof-urfuryl having a peroxide equivalent per gram of material of not less, than 80x10-*.

5. Peroxidized di-(tetrahydrofurfuryl) maleate having a peroxide equivalent per gram of material of not less than 80 10 6. Peroxidized di-(tetrahydrofurfuryl) succinate having a peroxide equivalent per gram of material of not less than 80X 10-.

MAYNARD C. AGENS.

maleate I 

